Detergent compositions containing sulfonio carboxylates

ABSTRACT

R1 IS C19-C18 ALKYL R2 IS C1-C4 ALKYL OR HYDROXYALKYL N IS 1-12.   R1-S(+)(-R2)-(CH2)N-COO(-)   DETERGENT COMPOSITIONS CONTAINING SULFONIO CARBOXYLATES, HAVING THE FORMULA SET FORTH BELOW, AND ALKALINE BUILDER SALTS ARE ESPECIALLY USEFUL IN COOL WATER DETERGENCY:

United States Patent 3,578,601 DETERGENT COMPOSITIONS CONTAININGSULFONIO CARBOXYLATES Arnon O. Snoddy, Cincinnati, and Francis L. Diehland Howard F. Drew, Wyoming, Ohio, assignors to The Procter & GambleCompany, Cincinnati, Ohio No Drawing. Original application Aug. 23,1966, Ser. No. 574,469. Divided and this application Nov. 12, 1968, Ser.No. 794,448

Int. Cl. 'C11d 3/04, 1/18 US. Cl. 252-135 8 Claims ABSTRACT OF THEDISCLOSURE Detergent compositions containing sulfonio carboxylates,having the formula set forth below, and alkaline builder salts areespecially useful in cool water detergency:

R1 is C o-C1 R is C -C alkyl or hydroxyalkyl n is 1-l2.

This application is a division of application Ser. No. 574,469, filedAug. 23, 1966, now abandoned.

This invention relates to sulfonic carboxylates and detergentcompositions containing same which are especially effective in coolwater. The term cool water as used in describing this invention isintended to mean aqueous washing solutions having a temperature within arange of from about 40 F. to about 95 F. This temperaturecharacterization more generally is intended to mean temperaturessubstantially below those which are commonly associated with the usualhousehold parlance of hot water.

Some garments or fabrics cannot be washed in hot water, i.e., say inexcess of about 110 F., without running the risk of damaging thematerial by shrinkage or altering the handle or feel of the fabric or byadversely affecting dyes or by increasing wrinkling in wash-and-wear orminimum care garments. For such laundering situations fabric andmaterial manufacturers recommend the use of cool water. Conventionaldetergents, however, are known to be less effective as cleaning agents,i.e., removing soil, in cool aqueous solutions. There is no questionthat the presently available detergent compositions can be used undersuch circumstances but with varying degrees of successful cleaningresults. To compensate for the poorer cleaning performance, consumersare generally inclined to use excessive amounts of the detergentcompositions. Such economic Waste is unfortunate but has been necessaryprior to the present invention due to the lack of detergent compositionswhich are specially formulated to be effective cleaning agents in coolwater.

It is an object of this invention to provide novel detergent compoundsand detergent compositions containing same which are especiallyeflfective in cleaning soiled fabrics in cool aqueous washing solutionsand a method for using such a composition in laundering with cool water.

Other objects will be readily apparent to those skilled in the art froma review of the following detailed description of the present invention.

This object of the present invention is achieved with novel sulfoniocarboxylate detergent compounds having the general formula noted belowand built detergent compositions containing same:

R is an alkyl group containing from 10 to 18 carbon atoms; R is an alkylor hydroxy alkyl group containing 3,578,601 Patented May 11, 1971 from 1t0 4 carbon atoms; 11 ranges from 1 to 12. The detergent compositions ofthis invention contain a sulfonio carboxylate of this class and a watersoluble inorganic alkaline builder salt, a water soluble organicalkaline sequenstrant builder salt or mixtures thereof, the ratio ofweight of the detergent to the builder salt being in the range of fromabout 4:1 to 1:20.

It has been surprisingly discovered that certain sulfonio carboxylatecompounds having the formula set forth above possess unusually effectivecleaning power in aqueous solutions having the cool temperatures definedabove. These unexpected cleaning properties of the zwitterioniccompounds of this invention are demonstrated by the experimental datapresented below. Of the sulfonio carboxylate detergent compoundsdescribed herein, best cool Water cleaning results are obtained when Ris tetradecyl or hexadecyl, R is methyl and n is 3, i.e., 4-(S-methyl-S-alkyl sulfonio) butyrate, wherein alkyl is C C The sulfonio carboxylatecompounds to which the present invention pertains can be prepared byfirst reacting a suitable n-alkyl mercaptan, which contains and suppliesthe R moiety, with a suitable monocarboxy derivative, which supplies the(CH moiety, such as an alkenyl carboxylic acid, alkenyl nitrile orlactone, each containing 1-12 carbon atoms. The resulting thia acidintermediate is then reacted in a second reaction with a lower alkyl orhydroxyalkyl halide, such as iodide, which contains and supplies the Rmoiety.

The product resulting after the second reaction is the acid halide,e.g., the acid iodide, of the sulfonio carboxylate, a form suitable forstorage, i.e.,

where X is a halide, such as Cl-, Bror I. In the usual washing pH rangesof 8 to 12, preferably 9.5 to 11.5, the acid halides are convertedquantatively to the zWitterionic form of the sulfonio carboxylate asillustrated by the formula above. An equal molar amount of a halidesalt, e.g. NaI, will then accompany the zwitterionic. While such a saltwill not adversely effect performance it can be separated by ordinarymethods from the zwitterionic.

The first reaction with the alkyl mercaptan takes place in a suitableinert solvent such as benzene or acetone, preferably at refluxconditions. The second reaction takes place readily with simple solutionof the thia acid intermediate in the alkyl halide at room temperatures.

The following examples illustrate the preparation of the compounds ofthis invention, but are not limitative thereof.

EXAMPLE I Preparation of C H S (CH2)3C O OH I- n-Hexadecyl mercaptan(52.0 g., 0.20 mole), 3-butenoic acid (17.2 g., 0.20 mole), andazo-bis-isobutyronitrile (1 g.) were refluxed in 500 m1. of benzene forthree hours. On cooling, the resulting S-thiaheneicosanoic acidcrystallized and was filtered. This acid was recrystallized from acetonegiving 66 g., 93% yield, of white crystals melting at 65.5 C.

S-thiaheneicosanoic acid (27.0 g., 0.078 mole) was then dissolved in 50ml. of iodomethane and let stand overnight. The resulting yellowcrystalline mass was filtered and the crystals washed with petroleumether. Recrystallization from acetone-ethanol gave 26.5 g., yield, ofwhite crystalline 3-carboxypropylhexadecylmethylsulfonium iodide, M.P.94-96". This acid iodide salt is readily converted to 4(S-methyl,S-hexadecyl sulfonio) having a pH of 1 0.

butyrate by dissolving it in an aqueous alkaline solution EXAMPLE II rPreparation of 0151129; (CH2)3C O OH I n-Tetradecyl mercaptan (55 g.,0.25 mole), S-butenenitrile (17.0 g., 0.25 mole), andazo-bis-isobutyronitrile (1 g.) were refluxed in acetone for 8 hours.The solvent was removed from the resulting S-thianonadecanonitrile underaspirator vacuum, the residual oil mixed with 400 ml. of 50% aqueousethanol containing 50 g. of sodium hydroxide, and the two-phase systemrefluxed for 8 hours. The resulting single phase system was cooled to-10 C. and acidified with sulfuric acid. The resulting fiocculentprecipitate of S-thianonadecanoic acid was filtered, washed with two-100ml. portions of water, and recrystallized from 2:1 acetone-water giving53 g., 67% yield from n-dodecyl mercaptan, of white crystals melting at64- 645 C.

S-thianonadecanoic acid (8.0 g., 0.025 mole) was dissolved in 25 ml. ofiodomethane and let stand 64 hours. The resulting yellow crystallinemass was filtered and recrystallized from hexane-acetone to give 9.1 g.,79% yield, of 3 carboxypropylmethyltetradecylsulfonium iodide. This acidiodide salt is readily converted to 4(S- methyl, S-tetradecyl sulfonio)butyrate by dissolving it in an aqueous alkaline solution at pH 10.

EXAMPLE III r Preparation of 012E253 (CH2)3C O OH I n-Dodecyl mercaptan(40.4 g., 0.20 mole) was dissolved in 100 ml. of methylcellosolvecontaining 11.6 g. (0.20 mole) of sodium methoxide and 34.4 g. (0.40mole) of 'y-butyrolactone. The reaction mixture was heated at reflux for36 hours, cooled, and acidified with an excess of 2 N hydrochloric acid.The copious white solid was filtered, washed with water, and taken up in500 ml. of ether. The ether was washed with five 100 ml. portions ofwater, dried, and evaporated under aspirator vacuum giving 14.2 g., 25%yield, of S-thiaheptadecanoic acid as white crystals, melting at 6263 C.

This crude acid was dissolved in 50 ml. of iodomethane and let standovernight. The resulting crystalline mass was filtered andrecrystallized from ether containing methanol to give 21.2 g., 97%yield, of 3-carboxypropylmethylsulfonium iodide melting at 95-96 C. Thisacid iodide salt is readily converted to 4(S-methyl, S-dodecyl sulfonio)butyrate by dissolving it in an aqueous alkaline solution having a pH of10.

EXAMPLE IV i Preparation of (3 11252 0 H2 (EH20 O O H I n-Dodecylmercaptan (20 g., 1.0 mole) was dissolved in 1000 m1. of a 1 molarsolution of sodium ethoxide in ethanol and fl-propiolactone (72 g., 1.0mole) added dropwise with cooling. Stirring was continued for 30minutes, whereupon the whole reaction solution crystallized. Thecrystalline mass was acidified with hydrochloric acid and the resultingaqueous ethanol solution extracted with three 400 ml. portions ofchloroform. The chloroform solution was dried and the solvent removedunder aspirator vacuum giving 141.5 g., 59% yield, of crude4-thiaoctadecanoic acid with melting point 59- 61.

A 54.8 g. (0.20 mole) sample of this crude acid was dissolved in 100 ml.of iodomethane and let stand 24 hours. The resulting crystalline masswas filtered, Washed with petroleum ether, and recrystallized fromacetone giving 61 g., 73% yield, of white crystals of 3-carboxy- 4ethyldodecylmethylsulfonium iodide melting at 108- 109 C. This acidiodide is readily converted to 3(S methyl, S-dodecyl sulfonio)propionate by dissolving it in an aqueous alkaline solution at pH 10.

Other sulfonio carboxylates of the class of compounds of this inventioncan be prepared in similar fashions selecting appropriate reactants toform the particular compounds desired. For example, pentanolactone orhexanolactone can be employed to prepare sulfonio carboxylates wherein nin the general formula is 4 or 5.

While the class of sulfonio carboxylate compounds just described can beemployed alone as cool water detergent compounds on easily cleanablematerials, more outstanding performances are obtained when they aremixed with other ingredients which enhance or build the cleaning powerof detergent compounds, i.e., so-called builders or detergency-enhancingcompounds. Such built or heavyduty detergency is essential withhard-to-clean, heavily soiled fabrics such as heavily soiled cottonfabrics. According to the present invention, therefore, the sulfoniocarboxylate detergent compounds are preferably used in conjunction withsuch other ingredients which substantially improve cleaning power. Whilethe term builder is used herein in its singular form, the term isintended to cover mixtures of such compounds also.

The present invention also pertains to detergent compositions consistingessentially of a water soluble inorganic alkaline builder salt or awater soluble organic alkaline sequestrant builder salt, or mixturesthereof, and a member of the class of sulfonio carboxylate detergentcompounds having the general formula described above, which compositionconsists essentially of the detergent compound and a builder material ina ratio by Weight of detergent to builder of about 4:1 to about 1:20.The preferred ratio of the detergent to builder is 1:1 to about 1:10.The ratios and percentages referred to herein are all by weight unlessotherwise noted.

The built detergent compositions of this invention can be prepared asgranular, tablet, or liquid compositions and perform effectively. Withinthe above detergent to builder ratio range, granular and tabletcompositions offering outstanding cool water washing performance cancontain from 4% to 50% by weight of the sulfonio carboxylate detergentcompound, the balance comprising essentially a selected builder materialor mixtures of builders and any optional ingredients employed. Preferredgranular and tablet compositions contain from about 15% to about 35% byweight of the sulfonio carboxylate detergent with the balance comprisingthe essential builder materials and other ingredients. On the otherhand, built liquid detergents prepared according to the presentinvention have a slightly modified composition to compensate for therequirement of a liquid vehicle. Such liquid compositions can containfrom about 2% to 25 by weight of the sulfonio carboxylate detergent,preferably from about 8% to about 18%, with the remainder comprisedessentially of builder ingredients, and, of course, a liquid vehicle asdescribed below. The ratio set forth above between the detergent andbuilder applies equally to all physical forms of the composition.

Water soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e.g., triethanol ammonium, salts of thesematerials can also be used. Specific examples of suitable salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumand potassium pyrophosphate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodiumorthophosphate and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built granular and tablet compositions and alkalimetal pyrophosphates for built liquid compositions. Potassium is thepreferred alkali metal used in liquid compositions and sodium finds bestapplication for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used inthis invention alone or in admixture are alkali metal, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminetetraacetate, sodium and potassiumN-(Z-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassiumnitrilotriacetates and sodium, potassium and triethanolammonium N(2-hydroxyethyl nitrilodiacetates. Mixed salts of these polycarboxylatesare also suitable. The alkali metal salts of phytic acid, e.g., sodiumphytate are also suitable as organic alkaline sequestrant builder salts(see US. Pat. 2,739,942).

Polyphosphonates are also valuable builders in terms of the presentinvention including specifically sodium and potassium salts ofethane-l-hydroxy-l, l-diphosphonic acid, sodium and potassium salts ofmethylene diphosphonic acid, sodium and potassium salts of ethylenediphosphonic acid, and sodium and potassium salts ofethane-1,1,2-triphosphonic acid. Other examples include the alkali metalsalts of ethane-Z-carboxy-l,l-diphosphonic acid,hydroxymethanediphosphonic acid, carbonyldiphosphonic acid,ethane-l-hydroxy 1,1,2-triphosphonic acid,ethane-Z-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane 1,1,2,3 tetraphosphonic acid, andpropane-1,2,2,3-tetraphosphonic acid.

Besides the builders being used in the form of mixtures it is alsopossible according to the present invention to use the sulfoniocarboxylate compounds of this invention in combination with othercleaning agents such as anionic, nonionic, ampholytic and otherzwitterionic organic detergent compounds. When it is desired to use suchsulfonio carboxylate compounds in combination with other detergentcompounds, they are preferably utilized with anionic detergents becauseof the sudsing characteristics of the latter. The ratio of the sulfoniocarboxylate to such other detergent compound is about 10:1 to 1:5. If itis desired to use such a sulfonio carboxylate in admixture with anotherdetergent compound as the active portion of a cleaning composition, theratio of such a mixture to the builder salt should be within thepreviously prescribed range of 4:1 to 1:20. A composition prepared alongthese lines can contain from 4% to 50% of such a mixture and 5% to 85%of a builder salt selected from water soluble inorganic alkaline buildersalts, Water soluble organic sequestrant builder salts, and mixturesthereof, within the prescribed ratio range.

Examples of anionic soap detergents which can be used in admixture withthe sulfonio carboxylate detergent, if desired, are the sodium,potassium, ammonium and alkylolammonium salts of higher detergent rangefatty acids (C C Particularly useful are the sodium and potassium saltsof the mixtures of fatty acids derived from coconut oil and tallow,i.e., sodium or potassium tallow and coconut soap. Examples of suitableanionic organic non-soap detergents in the form of their Water solublesalts are: alkylglycerylethersulfonates; alkyl sulfates; alkylmonoglyceride sulfates or sulfonates; alkylpolyethenoxy sulfates;acylsarcosinates; acyl esters of isethionates; N- acyl-N-methyltaurides, alkylbenzenesulfonates wherein the alkyl substituent isstraight chain or branched chain; sulfonated cc olefins; alkylphenolpolyethenoxy sulfonates. In these compounds the alkyl and acyl groups,respectively, contain to carbon atoms. They are used in the form ofwater soluble salts, the sodium, potassium, ammonium, andalkylolammonium salts, for example. Specific examples are: sodium laurylsulfate, sodium tallow alkyl sulfate; sodium salt of sulfonated atridecene; potassium N-methyl-N-lauroyl tauride; triethanolammoniumtetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.

Examples of nonionic organic detergents which can be used in thecompositions of this invention, if desired, are: polyethylene oxidecondensates of alkylphenols wherein the alkyl group contains from 8 to15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is presentin a molar ratio of ethylene oxide to alkylphenol in the range of 3:1 to20:1; condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylene diamine wherein themolecular weight of the condensation products ranges from 5000 to11,000; the condensation products of from about 5 to 30 moles ofethylene oxide with one mole of a straight or branched chain aliphaticalcohol containing from 8 to 18 carbon atoms, e.g., condensationproducts of 6 moles of ethylene oxide with one mole of lauryl alcohol;higher alkyl di-lower alkyl amine or phosphine oxides, e.g.,dodecyldirnethylamine oxide or dodecyldimethyl phosphine oxide; alkylmethyl sulfoxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight chain or branched and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic water solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate. Examples of compoundsfalling within this definition are sodium-3-dodecylaminopropionate, 3 (Nmethyl N hexadecyl amine) Z-hydroxy propane-l-sulfonate and its d0-decyl homolog, sodium 3-dodecylaminopropane sulfonate,dodecyl-beta-alanine, N-alkyltaurines such as the one prepared byreacting the dodecylamine with sodium isethionate according to theteaching of US. Pat. No. 2,658,072, N-higehr alkyl aspartic acids suchas those produced according to the teaching of US. Pat. No. 2,43 8,091,and the products sold under the trade name Miranol and described in US.Pat. No. 2,528,378.

Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and ternarysulfonium compounds, in which the aliphatic radical may be straightchain or branched, and wherein one of the aliphatic substituentscontains from 10 to 18 carbon atoms and one contains an anionic watersolubilization group, e.g., carboxy, sulfo, or sulfato. Examples ofcompounds falling within this definition are: 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate and thecorresponding dodecyl and tetradecyl homologs and 3 (N,Ndimethyl-N-dodecylammonio)-propane-1-sulfonate and the correspondinghexadecyl and tetradecyl homologs.

The discovery that the compositions containing members of the class ofcompounds described in this invention show exceptional cool waterdetergency was unpredictable in view of the fact that there is, as yet,virtually no generally accepted theory or background information on themechanics of cool water detergency. Moreover, cleaning agents such assodium tallow alcohol sulfate or sodium dodecylbenzenesulfonate, forexample, which are good hot water (-140 F.) detergent compounds exhibita minimum of cleaning activity in cool water. One would be led to assumethat the sulfonio carboxylate compounds of the present invention shouldbe, comparatively speakmg, as poor as any other conventional detergentcompounds when used in cool water; certainly there is no reason toexpect that they would behave otherwise. As has been discovered,however, the compositions containing the sulfonio carboxylate compoundsof this invention are more effective in cool water than some of thecommonly used commercially available detergent compositions are in hotwater. It can, therefore, be seen that the structure of a givendetergent compound which is etfective in hot water has little or nodiscernible relation to the effectiveness of such compounds in coolwater.

It has also been found that maximum cleaning occurs with thecompositions of this invention when the pH of the washing solution, atcool water temperatures as herein defined is within the range of fromabout 8 to about 12 with the preferred pH range being 9.5 to 11.5 Usingnormal amounts of water for washing, the desired pH of the solution canbe obtained by incorporating into the compositions of this invention anormal amount of a strongly alkaline material such as sodium silicate,i.e., up to about by weight. The silicate acts as a buffer and also as acorrosion inhibitor.

A laundering method incorporating the discovery of the present inventioncan be practiced in a number of different ways. Preferably the washingstep is followed by rinsing and drying the fabrics. The washing solutioncan be prepared by adding the granular, tablet or liquid detergentcomposition prepared according to this invention to any container whichcontains cool water at a temperature ranging from about 40 F. to about95 F., usually about 80 F. The detergent concentration in solution canrange from about .05 to 50% by total weight In the usual washingoperation and should be added in sufiicient amount to provide aconcentration of at least 0.005% of the sulfonio carboxylate detergentcompound. The fabrics can be added to the container or washer before orafter the washing solution is added. As is usual in a washing step, thefabrics are then agitated in the detergent solution. While the period oftime may vary, an

automatic agitator type washer, generally employs a washing cycle whichranges from 8 to minutes. In special situations, such as hand washing inbasins, pools or streams, higher composition concentrations can beemployed including solutions or pastes of up to 5%, or even and higher.

After the washing step, the washing liquor is drained off or the fabricsare separated from the liquor and thereafter the fabrics are rinsed inclean water. The fabrics can be rinsed as many times as desired in orderto insure that washing liquor is removed. Using an automatic washer, ithas been found that about one or more spray rinses and one deep rinseare usually sufiicient for this purpose. Between and after rinsingsteps, the bulk of the rinse Water is usually drawn from or spun out ofthe fabrics. After rinsing, the fabrics are dried. Although rinsing anddrying are usual and desirable steps, the important advantage of theinvention is achieved in the washing step.

The surprisingly eifective cool water performance char acteristics ofthe sulfonio carboxylate compounds described herein are demonstrated byconducting the detergency tests described as follows:

Naturally soiled fabric swatches (desized cotton print cloth) werewashed for ten minutes in an 80 F. aqueous solution of a detergentcomposition having a pH of 10 and containing 7 grains equivalent CaCOhardness per gallon. Detergent compositions were prepared con tainingonly basic essentials, i.e., a detergent compound and a buildercompound. The detergent compounds were representative sulfoniocarboxylates. The builder compound in each composition was sodiumtripolyphosphate. The sulfonio carboxylate compounds in the form oftheir hydrogen iodide salts were: 4(S-methyl, S-dodecyl sulfonio)butyrate (MDSB) 4(S-methyl, S-tetradecyl sulfonio) butyrate (MTSB)4(S-methyl, S-hexadecyl sulfonio) butyrate MHSB). In the alkalinewashing solution, the zwitterionic form of the sulfonio carboxylateformed with an equal molar amount of NaI. The concentration by weight inthe washing solution of the detergent compound in its zwitterionic formwas 02%; the concentration of the builder was .06%

These compositions were tested in two separate tests for their soilremoval properties. Soil removal, expressed as a percentage of the soiloriginally present on the soiled swatches, was determined. The amountsof soil present (a) on the cloth swatches after washing and drying and(b) on similar unwashed swatches were determined by solvent extraction;

8 Compound: Soil removal, percent MDSB 39.6-51.9 MTSB 50.1-62.8 MHSB58.4-59.8

The MTSB and MHSB detergent compositions gave results in these tests, inwater at P. which were almost as good as results obtained with a formulawherein sodium tetrapropylenebenzenesulfonate (ABS) was used as acleaning agent at a higher, .03% level, in a washing solution having atemperature of 140 F. Moreover, such sodiumtetrapropylenebenzenesulfonate compositions at 80 F. have soil removalgrades in the range of 40% to 45%.

Excellent performance of the preferred MTSB and MHSB at 80 F. ascompared with ABS at 140 F. was also demonstrated in a washing testemploying soiled mens white dress shirts where the collars and cuffswere used as the basis for comparing cleaning ability of compo sitionsemploying these two detergent compounds.

Substantially the same performance advantages are observed by thehousewife when doing her home laundry in water ranging from 40 to 95 F.,particularly laundering heavily soiled cotton goods. Woolens, syntheticfibers and wash-and-Wear garments Washed in the same manner are cleanedas efficiently when washed according to the process of this inventionand using the compositions of this invention as they would be if theywere Washed in conventional detergent compositions at hot Watertemperatures, yet a minimum of shrinkage and wrinkling takes place andthe color and feel of the fabric are preserved to a greater extent.

While the compositions of this invention are outstandingly effective inwater at a temperature ranging from 40 F. to 95 F. the preferredtemperature range is about 60 F. to F. Below about 60 F. it has beenfound that the granular detergent compositions of this invention aresomewhat slower to dissolve, consequently it is preferred to use liquidcompositions at such lower temperatures.

The following compositions further illustrate the manner in which theinvention can be practiced; they provide improved cool water detergencycharacteristics similar to that demonstrated in the soil removalcomparison set forth above. The pHs of each of the compositions inaqueous solutions ranged from 9.5 to 11.5 at concentrations of about0.25%. Included are both liquid and granular formulations. Mixtures ofthe sulfonio carboxylates and other detergents can be used. The examplesare not to be construed as limiting the scope of the invention claimedhereinafter. These compositions are useful in automatic washers andconventional type washers employing cool water, 40 F. to F., as well ashand washing operations: (the examples are based on sulfoniocarboxylates from which the alkali metal halide salts are removed).

EXAMPLE V Solid-granules Percent Z-(S-methyl, S-dodecyl sulfonio)acetate 17.5 Sodium tripolyphosphate 50 Sodium silicate (Na O'.SiO=1:2.5) 10.0 Sodium sulfate 17.5 Moisture 5 EXAMPLE VI Compressedgranulestablet 3-(S-propyl, S-tetradecy1 sulfonio) propionate 31Tetrasodium pyrophosphate 52 Trisodiurn phosphate l0 Moisture 7 9EXAMPLE v11 Solidgranules Percent S-(S-(Z-hydroxyethyl), S-hexadecylsulfonio) pentanoate 32 Pentasodium ethane 1hydroxy-1,1,2-triphosphonate 64 Moisture 4 EXAMPLE VIII Solid-granules 3(N,N dimethyl-N-hexadecyl ammonio)-propanel-sulfonate 20 6-(S-propyl,S-dodecyl sulfonio)-hexanoate 25 Sodium tripolyphosphate 35 Sodiumcarbonate 10 Sodium silicate (Na O:SiO =1:2.5) Moisture 5 EXAMPLE 1XSolid--granules 8-(S-methyl, S-hexadecyl) octanoate 20 Sodium tallowalcohol sulfate 10 Trisodium ethane-Lhydroxy-l,1diphosphonate 20 Sodiumtripolyphosphate 10 Sodium nitrilotriacetate 10 Sodium sulfate 8 Sodiumsilicate (Na O:SiO -=1:2.5) l1 Moisture 11 EXAMPLE X Liquid 4-(S-methyl,S-decyl) butyrate 5.0 Sodium salt of SO -sulfonated 1:1 weight mixtureof a dodecene and on tetradecene 10.0 Tetrapotassium pyrophosphate 19.0Sodium silicate (Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5Carboxymethyl hydroxyethyl cellulose .3 Water Balanc EXAMPLE XI Liquid5-(S-(2-hydroxypropyl), S-dodecyl sulfonio (pentanoate 6.0 Sodium(linear) dodecyl benzene sulfonate 6.0

Hexapotassium propane-1,1,3,3-tetraphosphonate 20.0

Sodium silicate (Na O:SiO =1:l.6) 3.8 Potassium toluene sulfonate 8.5Carboxymethyl hydroxymethyl cellulose .3 Water Balanc EXAMPLE XIISolidgranules 4(S-propyl, 3-dodecyl sulfonio) butyrate 5 Condensationproduct of 10 moles of ethylene oxide and one mole of tallow fattyalcohol 5 Sodium (linear) tridecyl benzene sulfonate 10 Dodecyldimethylphosphine oxide 5 Coconut oil soap 5 Sodium tripolyphosphate 50Tetrasodium ethylene diamine tetraacetate 20 azole or ethylene thioureamay be added in amounts up to about 1%. Fluorescers, perfume, bleachingagents, color, antiredeposition agents, antibacterial agents, thickeningagents, opacifiers, and blending or viscosity control agents, while notessential in the compositions of this invention, may also be added.

While the present invention finds exceptional application in cool waterwashing situations, the compositions described herein can also be usedin conjunction with warm and hot water.

What is claimed herein is:

1. A detergent composition having superior cleaning ability in aqueoussolutions having a temperature within a range of from about 40 F. toabout 95 F. consisting essentially of (1) from about 4% to about 50% byweight of a sulfonio carboxylate detergent compound of the generalformula wherein R is an alkyl group containing from 12 to 16 carbonatoms and R is methyl; or an acid halide salt thereof; and (2) fromabout 50% to about 95% by Weight of a builder material selected from thegroup consisting of water-soluble inorganic alkaline builder salts,Water-soluble organic alkaline sequestrant builder salts, and mixturesthereof, the ratio by weight of said detergent compound to said buildermaterial being in the range of about 4:1 to about 1:20.

2. The detergent composition of claim 1 wherein the ratio of saiddetergent compound to said builder is from 1:1 to about 1: 10, by weightand the sulfonio carboxylate compound is 4-(S-methyl, S-tetradecylsulfonio) butyrate.

3. The detergent composition of claim 1 in which the aqueous solutionhas a pH of from about 8 to about 12.

4. The detergent composition of claim 2 wherein the preferred pH rangeis between about 9.5 and 11.5.

5. The detergent composition of claim 4 wherein said builder material issodium tripolyphosphate.

6. A laundering process comprising the step of immersing soiled fabricsand garments into an aqueous solution having a temperature within therange of from about 40 to about 95 F. and a pH of from about 8 to about12, said aqueous solution containing at least about .05 by weight of thedetergent composition of claim 1.

7. The process of claim 6 wherein the detergent composition consistsessentially of from about 47 to about 50% by weight of the detergentcompouid 4(S-methyl-S- tetradecyl sulfonio) butyrate and from about 50%to about 96% by weight of the builder materal sodium tripolyphosphate,the ratio of said detergent compound to said builder material being inthe range of about 4:1 to about 1:20 and the pH is between about 9.5 and11.5.

8. A built detergent composition consisting essentially of 4 to 50% of amixture of the sulfonio carboxylate detergent compound of claim 1 and anorganic anionic detergent, the ratio of the sulfonio carboxylatecompound to said organic detergent being in the range of 10:1 to 1:5 andfrom 5 to of a builder material selected from the group consisting ofwater soluble inorganic alkaline builder salts, Water soluble organicalkaline sequestrant builder salts, and mixtures thereof.

References Cited UNITED STATES PATENTS 3,351,558 11/1967 Zimmerer 2521373,400,148 9/1968 Quimby 260-502.4 3,400,176 9/ 1968 Quimby 260-9322,813,898 1 1/ 1957 Gaertner 260-505 2,892,852 6/1959 Koenig et al260400 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant ExaminerUS. Cl. X.R. 252-137, 138, 152, 161

